Aqueous binder composition for mineral fibers

ABSTRACT

An aqueous binder composition for mineral fibers comprises: (a) a sugar syrup containing a reducing sugar and having a dextrose equivalent DE of at least 50 and less than 85; (b) a polycarboxylic acid component; (c) an amine component; and, optionally, (d) a reaction product of a polycarboxylic acid component (b) and an amine component (c).

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of U.S. application Ser. No.14/086,245, filed Nov. 21, 2013, which is a continuation of U.S.application Ser. No. 13/257,015, now U.S. Pat. No. 8,591,642, which is aNational Stage entry of International Application NumberPCT/EP2010/053645, filed Mar. 19, 2010; the entire disclosures of theseapplications are expressly incorporated by reference herein.

FIELD OF THE INVENTION

The present invention relates to an aqueous binder composition, a methodof producing said aqueous binder composition and to its use in themanufacture of bonded mineral fiber products. More specifically, thepresent invention relates to an aqueous binder composition produced fromcarbohydrate starting materials and to its use for bonding mineral fiberproducts.

BACKGROUND OF THE INVENTION

Mineral fiber products generally comprise man-made vitreous fibers(MMVF) such as, e.g., glass fibers, ceramic fibers, basalt fibers, slagwool, mineral wool and stone wool, which are bonded together by a curedthermoset polymeric binder material. For use as thermal or acousticalinsulation products, bonded mineral fiber mats are generally produced byconverting a melt made of suitable raw materials to fibers inconventional manner, for instance by a spinning cup process or by acascade rotor process. The fibers are blown into a forming chamber and,while airborne and while still hot, are sprayed with a binder solutionand randomly deposited as a mat or web onto a travelling conveyor. Thefiber mat is then transferred to a curing oven where heated air is blownthrough the mat to cure the binder and rigidly bond the mineral fiberstogether.

In the past, the binder resins of choice have been phenol/formaldehyderesins which can be economically produced and can be extended with ureaprior to use as a binder. However, the existing and proposed legislationdirected to the lowering or elimination of formaldehyde emissions haveled to the development of formaldehyde-free binders such as, forinstance, the binder compositions based on polycarboxy polymers andpolyols or polyamines, such as disclosed in EP-A-583086, EP-A-990727,EP-A-1741726, U.S. Pat. No. 5,318,990 and US-A-2007/0173588.

Another group of non-phenol/formaldehyde binders are theaddition/-elimination reaction products of aliphatic and/or aromaticanhydrides with alkanolamines, e.g., as disclosed in WO 99/36368, WO01/05725, WO 01/96460, WO 02/06178, WO 2004/007615 and WO 2006/061249.These binder compositions are water soluble and exhibit excellentbinding properties but may require expensive starting materials and, inparticular, a high proportion of expensive anhydride reactants in orderto achieve the desired water solubility, curing speed and curingdensity. Several of the above-mentioned patent publications thereforesuggest the use of cheaper carbohydrates as additives, extenders or asreactive components of the binder system.

SUMMARY OF THE INVENTION

It has now been found that further improvements both in production costsand in application properties such as curing speed, curing density,durability and humidity resistance may be achieved by using specifictypes of carbohydrates in binder production.

Thus, in a first aspect, the present invention relates to an aqueousbinder composition comprising:

-   (a) a sugar syrup containing a reducing sugar and having a dextrose    equivalent DE of at least 50 and less than 85;-   (b) a polycarboxylic acid component;-   (c) an amine component; and, optionally,-   (d) a reaction product of a polycarboxylic acid component (b) and an    amine component (c).

In a further aspect, the present invention relates to a method ofproducing a bonded mineral fiber product which comprises the steps ofcontacting the mineral fibers or mineral fiber product with an aqueousbinder composition as defined above, and curing the binder composition.

In accordance with another aspect of the present invention, there isprovided a mineral fiber product comprising mineral fibers in contactwith the cured binder composition defined above.

BRIEF DESCRIPTION OF THE DRAWING

In the accompanying drawing, FIG. 1 is a graph showing the water uptakein percent after 3, 10 and 14 days of several binder compositions setforth in the Examples below as a function of the dextrose equivalent DEof the sugar syrup present in the compositions.

DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS

The aqueous binder composition according to the present inventioncomprises:

-   (a) a sugar syrup containing a reducing sugar and having a dextrose    equivalent DE of at least 50, for instance, at least 60 or 65, and    less than 85, for instance, less than 80 or 75;-   (b) a polycarboxylic acid component;-   (c) an amine component; and, optionally,-   (d) a reaction product of a polycarboxylic acid component (b) and an    amine component (c).

Sugar Component (a)

Glucose is formed in plants from carbon dioxide absorbed from the airusing sunlight as energy source. Part of the glucose is polymerised intolong chains of glucose and stored as starch in granules as a reserve.Another glucose polymer found in plants is cellulose. Compared tocellulose, starch is made up of alpha-glucosidic bonds, which result inhelix-shaped molecules, while cellulose is build with beta-glucosidicbonds giving straight molecules and a fibrous structure.

For commercial manufacture of crystalline dextrose, an aqueous slurry ofstarch is subjected to hydrolysis by means of heat, acid or enzymes.Depending on the reaction conditions employed in the hydrolysis ofstarch, a variety of mixtures of glucose and intermediates is obtainedwhich may be characterized by their DE number. DE is an abbreviation forDextrose Equivalent and is defined as the content of reducing sugars,expressed as the number of grams of anhydrous D-glucose per 100 g of thedry matter in the sample, when determined by the method specified inInternational Standard ISO 5377-1981 (E). This method measures reducingend groups and attaches a DE of 100 to pure glucose (=dextrose) and a DEof 0 to pure starch.

Hydrolytic cleavage of the starch may be stopped at different stages ofthe process resulting in carbohydrate mixtures (sugar syrups) havingdifferent DE numbers, i.e. having different molecular weightdistribution and different reactivity. The starting point for theprocess is a purified starch milk, i.e. a native starch such as corn orcassava potato which has been treated by e.g. cleaning, milling, washingand made into a slurry preparation.

Only glucose syrup of high DE can crystallize easily and yield a productin powder or granular form. A most popular crystallized product isdextrose monohydrate with application in medicine and chewing tablets.Dextrose monohydrate is pure glucose (DE 100).

With lower DE numbers, the syrup gradually loses its tendency tocrystallize. Below approx. 45 DE, the syrup can be concentrated into astable, non-crystallizing liquid, for instance, standard 42 DE syrupwhich finds wide spread use in canned fruit preserves, ice cream, bakeryproducts, jam, candy, and all kinds of confectionery.

The present invention is based on the surprising finding that the morehigh-molecular components of the starch hydrolysate (sugar syrup) do notcontribute significantly to the formation of the cross-linked bindernetwork. Furthermore, it has been shown that the high-molecular speciesin the crude hydrolysate do not negatively influence the binderproperties in terms of hydrolytic stability and durability, provided thedextrose equivalent is not below 50. Also, certain sugar syrups of thehydrol and molasses type show these characteristics. All thesehigh-molecular component sugar syrups fall into a preferred interval forthe DE value according to the present invention.

The requirements of a binder system suitable for binding a mineral woolproduct so as to provide an adequate product and process for making sucha product are many and varied in terms of physical parameters, some ofwhich are explained below.

The viscosity and the content of large polymers in a sugar syrupgenerally may decrease with an increasing DE value. A large content ofpolymers should preferably be avoided for a mineral wool binder becausethis will provide a more sticky binder resulting in stickiness of theformed mineral wool mat or binder-containing web to the manufacturingequipment such as e.g. the forming chamber walls, the travellingconveyors, rollers and pendulums.

The solubility of the binder solution containing a sugar syrup mayincrease with increasing DE value. The binder solution must besufficiently water soluble to provide a homogenous distribution of thebinder on the mineral fibers making up the mineral wool mat or web to becured.

On the other hand, a sugar syrup will generally result in a browningwhich is more pronounced with increasing DE value, thus leading tounwanted aesthetical appearance for a mineral wool product containing abinder system with sugar syrups, at least for some applications of themineral wool product. Sugar syrups with too high a DE will also have atendency to add to the boiling point elevation effect of the bindercompared to low DE sugar syrups. The binder composition for a mineralwool web should preferably not have too high a boiling point since thiswill lead to an increase in curing time and thus result in higher curingtemperatures and/or a physically longer curing oven length to provide alonger curing time.

The aqueous binder composition containing a sugar syrup will lower thewater activity when increasing the DE value for the sugar syrup, and oneof the effects of a low water activity may be that the binder issusceptible to moisture migration. This may create an unwanted uptake ofmoisture in the binder droplets in the uncured mineral wool web.

It has been found that a aqueous binder composition comprising a sugarsyrup containing a reducing sugar having a dextrose equivalent DE of 50to less than 85 will provide excellent products fulfilling the manydemands to the binder in a mineral wool production line and the demandsto the products obtained by using the binder.

The sugar syrup employed as component (a) contains a reducing sugar andmay additionally contain a carbohydrate compound that yields one or morereducing sugars in situ under thermal curing conditions. The sugar orcarbohydrate compound may be a monosaccharide in its aldose or ketoseform, including a disaccharide, a triose, a tetrose, a pentose, ahexose, or a heptose; or a di-, oligo- or polysaccharide; orcombinations thereof. Specific examples are glucose (=dextrose), starchhydrolysates such as corn syrup, arabinose, xylose, ribose, galactose,mannose, fructose, maltose, lactose and invert sugar. Compounds such assorbitol and mannitol, on the other hand, which do not contain or supplyaldehyde or ketone groups, are less effective in the instant invention.

The sugar syrup may be prepared by any known process. FIG. 1 is adiagram showing the sequence of steps employed in typical embodiments ofsuch conventional methods. This diagram was published by theInternational Starch Institute, Science Park Aarhus, Denmark, and isavailable under www.starch.dk “Starch Sweeteners”.

Crude Hydrolysate from Starch-Based Glucose Refining and Treated CrudeHydrolysate from Starch-Based Glucose Refining

An example of a typical commercial process involving acidic hydrolysiscomprises adding an acid such as hydrochloric acid to a water slurry ofstarch (purified starch milk) in order to acidify it before cooking. Theacidified slurry is then heated to the desired liquefaction temperatureand kept at that temperature until the required degree of hydrolysis hasbeen obtained. The combination of reaction time, temperature andconcentration of acid controls the degree of hydrolysis. Afterneutralization of the acid, the crude hydrolysate may be filtered andrefined by means of activated carbon and/or ion exchange in order toremove impurities, discoloration and by-products formed during thehydrolysis and to give a so-called treated crude hydrolysate. Dependingon raw material and end product requirements, various filtration steps,active carbon treatment steps and ion exchange steps for deionizationetc. may be added to the process. Any sequence of refining steps may beemployed, for instance, (1) filtration/ion exchange/carbon treatment;(2) filtration/carbon treatment/ion exchange; and for very high quality(3) filtration/carbon treatment/ion exchange/carbon treatment.

Treatment of the crude hydrolysate may lead to a sugar syrup such as ahigh DE corn syrup (a high DE glucose syrup) having a DE of from 55 to70.

In certain instances, however, for instance, if the further reaction ofthe sugar component (a) requires an additional nitrogen source as areactant, it may be preferable to employ the sugar syrup (a) without anyprior removal of proteins and/or oils through refining. For instance, ina specific embodiment only ions (salts) are removed from the crudehydrolysate by ion exchange using cationic and/or anionic resinsresulting in an embodiment of a treated crude hydrolysate from thestarch-based glucose refining.

Hydrolysis with acid catalysts allows the manufacture of intermediateconversion products ranging from 35-55 DE. Intermediate and higherconversion products with DE from 28 up to 98 can be made by substitutingacid with enzymes. This is typically done in a two-step process. For thefirst step (liquefaction), thermo-stable a-amylase, or acid is used.After cooling and pH adjustment, a saccharification enzyme such asamyloglucosidase is employed. Except for a different holding time, pHand temperature, the processes are in principle the same, regardless ofthe catalyst. However, enzymes and acid break down the starchdifferently, resulting in different sugar composition of identical DE.

High fructose syrups are produced from refined high DE dextrose syrupsin an enzymatic process using isomerase immobilised on a resin whichenzymatically converts glucose to fructose. These syrups areconventionally referred to as HESS and are also suitable sugar syrupswhich may, for instance, be provided with a DE around 55.

Also, the commercially available wort syrups for beer brewing mayprovide a suitable sugar syrup for the binder composition.

Hydrol

In one specific embodiment of the present invention, “hydrol” isemployed as the sugar component (a). “Hydrol” is the mother liquor orresidual liquor remaining from the crystallization of dextrose fromdextrose syrup with a high concentration of dextrose, for instance, 55to 75% by weight of dextrose. Hydrol generally has a DE of from 72 to85. Hydrol is also often referred to as “starch molasses”.

As explained earlier, the usual commercial manufacture of crystallinedextrose involves subjecting a water slurry of starch to hydrolysis bymeans of heat in the presence of acid or an enzyme under controlledconditions of temperature, pH and time in the first stage of thehydrolysis usually referred to as liquefaction. This is followed by thesecond stage hydrolysis called saccharification where enzymes are usedunder a different set of controlled conditions of temperature, pH andtime. In an exemplary embodiment, the reaction is, for instance, allowedto continue until the starch has been hydrolyzed to produce a liquor ofabout 90-98 DE, preferably 90-93 DE, containing about 85-96% by weight,preferably about 85-90% by weight, of dextrose, measured on a dry basis,together with other sugars. When it is hydrolyzed as far as desired, theliquor is refined and evaporated to a concentration of 74-78% by weightof dry substance after which it is then cooled and seeded withcrystallized dextrose and allowed to develop crystals in awater-jacketed crystallizer. The dextrose crystals are subsequentlyseparated from the liquor, for instance, by centrifuging.

The mother liquor, known as first greens in current conventionalpractice, is subsequently concentrated to 74-78% by weight of drysubstance. This syrup, now known as the second sugar syrup or greens, isconcentrated and recrystallized in a manner similar to the first sugarsyrup and the resulting dextrose crystals centrifugally separated. Themother liquor from this second crystallization is typically concentratedto 71% by weight of dry substance. This syrup is known as “hydrol”.

Alternatively it is possible to recycle part of the mother liquid fromthe first crystallization back into the process at a stage before thefirst crystallization. In this case, only one crystallization stage isnecessary and hydrol is made by bleeding off some of the recycled motherliquor in the hydrol evaporation step.

The hydrol itself may be hydrolyzed with a mineral acid converting thebulk of the oligosaccharides to dextrose.

Molasses

In another specific embodiment of the present invention, molasses isemployed as a carbohydrate compound that yields one or more reducingsugars upon treatment with acids such as, e.g., sulfuric acid.

The term “molasses” as used herein generically embraces many types ofmolasses with varied sugar content and sugar type and other constituentsmaking up the molasses. Sugar cane and beet molasses products are by farthe most common types. Molasses have a typical total solids content of60-80% by weight.

The compositions stated below represent typical compositions of thedifferent types of molasses. As is often found with industrialby-products, the chemical composition of molasses shows wide variation.Its composition is influenced by factors such as soil type, ambienttemperature, moisture, season of production, variety, productionpractices at a particular processing plant, and by storage variables.

Cane molasses is a by-product in the manufacture or refining of sucrosefrom sugar cane. It may contain more than 46% by weight of total sugarsexpressed as invert sugar.

Beet molasses is a by-product in the manufacture of sucrose from sugarbeets. It may contain more than 48% by weight of total sugars expressedas invert sugar.

Citrus molasses is the partially dehydrated juices obtained from themanufacture of dried citrus pulp. It may contain more than 45% by weightof total sugars expressed as invert sugar. The canning of hearts, juice,and citrus concentrate leads to a pulp of e.g. peel, rag, and seed. Thisresidue or fresh pulp contains about 85% of moisture mostly as boundwater, or water of constitution. In one process for making citrusmolasses, addition of calcium salts to the fresh pulp liberates thebound water. One-half of the water is then removed by pressure. The pulpis dehydrated into dried citrus pulp. The press juice contains about 5%solids, mainly sugars. Evaporation of this material under partial vacuumto about one-thirteenth of the original volume results in a lightcolored sweet viscous syrup known to the feed industry as “citrusmolasses.”

Wood molasses is a by-product in the manufacture of pressed wood. It isthe concentrated soluble material obtained from the treatment of wood atelevated temperature and pressure with or without use of acids, alkalis,or salts. It contains pentose and hexose sugars, and may have a totalcarbohydrate content of not less than 55% by weight. Hemicelluloseextract is often referred to as wood molasses. The wood molassesproducts are also often described in the art as aqueous solublehemicellulose extracts of wood.

To convert cellulose into glucose, in one process, high temperatures andpressures are required when dilute acids are used. With concentratedacids, the process can be carried out at room temperature. Hemicelluloseis more easily converted into sugars. The hemicellulose from hardwood(e.g. maple and beech) yields a high percentage of pentoses, whilehemicellulose from softwood (e.g. pine and fir) yields a 1:1 mixture ofpentoses and hexoses.

In another process, hemicellulose from wood is solubilized by steamduring the manufacture of hardboard. This process is economical as itessentially does not require chemicals. The hemicellulose sugars areconcentrated or spray-dried and available under the name wood molasses.

The molasses may be hydrolyzed with a mineral acid converting the bulkof the disaccharides and oligosaccharides to dextrose.

in one embodiment, a sugar syrup of wood molasses is used as the sugarsyrup (a); the wood molasses is preferably used without having undergonean ion exchange refining step.

In another embodiment, a sugar syrup of wood molasses is used as thesugar syrup (a), wherein the wood molasses has been treated by refiningto be essentially free of calcium, potassium, sodium and chlorine.

Polycarboxylic Acid Component (b)

The polycarboxylic acid component (b) is generally selected fromdicarboxylic, tricarboxylic, tetracarboxcylic, pentacarboxylic, and likemonomeric polycarboxylic acids, and anhydrides, salts and combinationsthereof, as well as polymeric polycarboxylic acids, anhydrides,copolymers, salts and combinations thereof.

Specific examples of suitable polycarboxylic acid components (b) arecitric acid, aconitic acid, adipic acid, azelaic acid, butanetricarboxylic acid, butane tetracarboxylic acid, chlorendic acid,citraconic acid, dicyclopentadiene-maleic acid adducts,diethylenetriamine pentaacetic acid, adducts of dipentene and maleicacid, ethylenediamine tetraacetic acid (EDTA), fully maleated rosin,maleated tall-oil fatty acids, fumaric acid, glutaric acid, isophthalicacid, itaconic acid, maleated rosin oxidized to alcohol then carboxylicacid, maleic acid, malic acid, mesaconic acid, oxalic acid, phthalicacid, tetrahydrophthalic acid, hexahydrophthalic acid, terephthalicacid, sebacic acid, succinic acid, tartaric acid, aspartic acid,trimellitic acid, pyromellitic acid, trimesic acid, and anhydrides,salts and combinations thereof.

Amine Component (c)

In the preparation of the binder composition according to the presentinvention, an amine component (c) is used which adds to the amines whichmay already be present in the sugar component (a) in amounts sufficientto form the desired binder resin. Thus, unrefined sugar syrups whichhave not undergone any prior refining aiming at removal of proteinsand/or oils may be employed without addition of an amine component (c).

Suitable amine components (c) are, for instance, ammonia, ammoniumsalts, primary or secondary amines, alkanolamines and amino acids.

Specific examples of ammonium salts are ammonium chloride, ammoniumsulfate, ammonium phosphate and the ammonium salts of the polycarboxylicacids (b).

Specific examples of suitable primary and secondary amines are alkylamines and dialkyl amines like methyl amine, dimethyl amine, propylamine, butyl amine and polyamines like ethylene diamine

Specific examples of suitable alkanolamines are diethanolamine,triethanolamine, diisopropanolamine, triisopropanolamine,methyldiethanolamine, ethyldiethanolamine, n-butyldiethanolamine,methyldiisopropanolamine, ethylisopropanolamine,ethyldiisopropanolamine, 3-amino-1,2-propanediol,2-amino-1,3-propanediol, aminoethylethanolamine andtris(hydroxymethyl)aminomethane.

Specific examples of amino acids are glycine, alanine, valine, leucine,serine, lycine and arginine.

Urea and urea compounds such as cyclic ureas may also be used as asource for the amine component (c). The use of urea in the bindercomposition has the additional advantage of better fire properties ofthe cured binder in the mineral wool product.

Reaction Product (d) of Polycarboxylic Acid Component (b) and Amine (c)

In accordance with a specific embodiment of the present invention, thebinder composition comprises a water-soluble reaction product of apolycarboxylic acid component (b) and an amine (c) as an optionalcomponent (d). A particularly preferred embodiment of that typecomprises using the water-soluble reaction product of at least onecarboxylic anhydride and at least one alkanolamine as component (d).

Preferred alkanolamines for use in the preparation of optional bindercomponent (d) are alkanolamines having at least two hydroxy groups suchas, for instance, alkanolamines represented by the formula

wherein R¹ is hydrogen, a C₁₋₁₀ alkyl group or a C₁₋₁₀ hydroxyalkylgroup; and R² and R³ are C₁₋₁₀ hydroxyalkyl groups. Preferably, R² andR³, independently are C₂₋₅ hydroxyalkyl groups, and R¹ is hydrogen, aC₁₋₅ alkyl group or a C₂₋₅ hydroxyalkyl group. Particularly preferredhydroxyalkyl groups are β-hydroxyalkyl groups.

Specific examples of suitable alkanolamines are diethanolamine,triethanolamine, diisopropanolamine, triisopropanolamine,methyldiethanolamine, ethyldiethanolamine, n-butyldiethanolamine,methyldiisopropanolamine, ethylisopropanolamine,3-amino-1,2-propanediol, 2-amino-1,3-propanediol andtris(hydroxymethyl)aminomethane. Diethanolamine is the currentlypreferred alkanolamine.

The carboxylic anhydride reactant may be selected from saturated orunsaturated aliphatic and cycloaliphatic anhydrides, aromatic anhydridesand mixtures thereof, saturated or unsaturated cycloaliphaticanhydrides, aromatic anhydrides and mixtures thereof being preferred. Ina particularly preferred embodiment of the invention, two differentanhydrides selected from cycloaliphatic and/or aromatic anhydrides areemployed. These different anhydrides are preferably reacted in sequence.

Specific examples of suitable aliphatic carboxylic anhydrides aresuccinic anhydride, maleic anhydride and glutaric anhydride. Specificexamples of suitable cycloaliphatic anhydrides are tetrahydrophthalicanhydride, hexahydrophthalic anhydride, methyltetrahydrophthalicanhydride and nadic anhydride, i.e.endo-cis-bicyclo[2.2.1]-5-heptene-2,3-dicarboxylic anhydride. Specificexamples of suitable aromatic anhydrides are phthalic anhydride,methylphthalic anhydride, trimellitic anhydride and pyromelliticdianhydride.

In the above embodiment employing two different anhydrides, acombination of cycloaliphatic anhydride and aromatic anhydride isparticularly preferred, e.g. a combination of tetrahydrophthalicanhydride (THPA) and trimellitic anhydride (TMA). The molar ratio ofcycloaliphatic anhydride to aromatic anhydride is preferably within therange of from 0.1 to 10, more preferably within the range of from 0.5 to3.

In the preparation of binder component (d), the proportion of thealkanolamine and carboxylic anhydride reactants is preferably selectedsuch that the ratio of equivalents of amine plus hydroxy groups (NH+Oil)to equivalents of carboxy groups (COOH) is at least 0.4, more preferablyat least 0.6.

On the other hand, the properties of the final binder composition, suchas curing behavior, durability and humidity resistance are determined bythe total ratio of reactive groups present. Therefore, for optimumperformance, the ratio of equivalents of amine plus hydroxy groups(NH+OH) to equivalents of carboxy groups (COOH) in the final bindercomposition is preferably adjusted to 2.0 or less, more preferably to1.7 or less. in general, the final binder composition has an equivalentratio of (NH+OH)/(COOH) within the range of from 1.25 to 1.55.

The reaction between the alkanolamine and carboxylic anhydride reactantsis carried out in the usual manner, for instance, as described in WO99/36368, WO 01/05725, WO 02/06178, WO 2004/007615 and WO 2006/061249,the entire contents of which is incorporated herein by reference.

If appropriate, an additional acid monomer may be employed in thereaction and is preferably added to the reaction mixture before additionof the anhydride reactant. Specific examples of suitable acid monomersare di-, tri- and polycarboxylic acids such as adipic acid, citric acid,sebacic acid, azelaic acid, succinic acid, tartaric acid and trimelliticacid.

The reaction temperature is generally within the range of from 50° C. to200° C. In a preferred embodiment and, in particular, when two differentanhydrides are employed, the alkanolamine is first heated to atemperature of at least about 40° C., preferably at least about 60° C.,whereafter the first anhydride is added and the reaction temperature israised to at least about 70° C., preferably at least about 95° C. andmore preferably at least about 125° C., at which temperature the secondanhydride is added to the reaction mixture when substantially all thefirst anhydride has dissolved and/or reacted. Increasing the reactiontemperature from 70-95° C. to 100-200° C. allows a higher conversion ofmonomers to oligomers. In this case, a preferred temperature range is105-170° C., more preferably 110-150° C.

If water is added after the first anhydride has reacted, either togetherwith the second anhydride or before addition of the second anhydride orat the end of the reaction, in an amount to make the binder easilypumpable, a binder having an increased molecular weight (compared towater addition from the start) is obtained which still has a desiredpumpability, viscosity, and water dilutability and contains lessunreacted monomers.

In order to improve the water solubility and dilutability of the binder,a base may be added up to a pH of about 8, preferably a phi of betweenabout 5-8, and more preferably a pH of about 6. Furthermore, theaddition of a base will cause at least partial neutralization ofunreacted acids and a concomitant reduction of corrosiveness. Normally,the base will be added in an amount sufficient to achieve the desiredwater solubility or dilutability. The base is preferably selected fromvolatile bases which will evaporate at or below curing temperature andhence will not influence curing. Specific examples of suitable bases areammonia (NH.sub.3) and organic amines such as diethanolamine (DEA) andtriethanolamine (TEA). The base is preferably added to the reactionmixture after the reaction between the alkanol amine and the carboxylicanhydride has been actively stopped by adding water.

Other Components of Binder Composition

The binder compositions according to the present invention mayadditionally comprise one or more conventional binder additives. Theseinclude, for instance, curing accelerators such as, e.g.,β-hydroxyalkylamides; the free acid and salt forms of phosphoric acid,hypophosphorous acid and phosphonic acid. Other strong acids such asboric acid, sulfuric acid, nitric acid and p-toluenesulthnic acid mayalso be used, either alone or in combination with the just mentionedacids, in particular with phosphoric, hypophosphorous acid or phosphonicacid. Other suitable binder additives are silane coupling agents such as.gamma.-aminopropyltriethoxysilane; thermal stabilizers; UV stabilizers;emulsifiers; surface active agents, particularly nonionic surfactants;biocides; plasticizers; anti-migration aids; coalescents; fillers andextenders such as carbohydrates, clay, silicates and magnesiumhydroxide; pigments such as titanium dioxide; hydrophobizing agents suchas fluorinated compounds, mineral oils and silicone oils; flameretardants; corrosion inhibitors such as thiourea; urea; antifoamingagents; antioxidants; and others.

These binder additives and adjuvants may be used in conventional amountsgenerally not exceeding 20 wt. % of the binder solids. The amount ofcuring accelerator in the binder composition is generally between 0.05and 5 wt. %, based on solids.

Final Binder Composition

The aqueous binder composition according to the present inventionpreferably comprises 50 to 85 percent by weight of sugar syrup (a); 5 to25 percent by weight of polycarboxylic acid (b); and 1 to 8 percent byweight of amine (c), based on the total weight (dry matter) of bindercomponents (a), (b) and (c).

The aqueous binder composition generally has a solids content of from 1to 20 wt. % and a pH of 6 or greater.

Mineral Fiber Product

The mineral fibers employed may be any of man-made vitreous fibers(MMVF), glass fibers, ceramic fibers, basalt fibers, slag wool, rockwool, stone wool and others.

Suitable fiber formation methods and subsequent production steps formanufacturing the mineral fiber product are those conventional in theart. Generally, the binder is sprayed immediately after fibrillation ofthe mineral melt on to the airborne mineral fibers. The aqueous bindercomposition is normally applied in an amount of 0.1 to 10%, preferably0.2 to 8% by weight, of the bonded mineral fiber product on a dry basis.

The spray-coated mineral fiber web is generally cured in a curing ovenby means of a hot air stream. The hot air stream may be introduced intothe mineral fiber web from below, or above or from alternatingdirections in distinctive zones in the length direction of the curingoven.

The curing may take place in accordance with a Maillard-type reactionroute between two or more of the constituents of the binder composition.Preferably, there may be several reaction routes taking place during thecuring. Typically, the curing oven is operated at a temperature of fromabout 150° C. to about 350° C. Preferably, the curing temperature rangesfrom about 200 to about 300° C. Generally, the curing oven residencetime is from 30 seconds to 20 minutes, depending on, for instance, theproduct density.

If desired, the mineral wool web may be subjected to a shaping processbefore curing. The bonded mineral fiber product emerging from the curingoven may be cut to a desired format e.g., in the form of a batt. Thus,the mineral fiber products produced may, for instance, have the form ofmats, baits, slabs, sheets, plates, strips, rolls, granulates and othershaped articles. In accordance with the present invention, it is alsopossible to produce composite materials by combining the bonded mineralfiber product with suitable composite layers or laminate layers such as,e.g., metal, glass surfacing mats and other woven or non-wovenmaterials.

The following examples are intended to further illustrate the inventionwithout limiting its scope.

EXAMPLE 1 Binder Composition Containing a Crude Starch Hydrolysate

100 g of crude starch hydrolysate having a concentration of 70% byweight of dry substance is obtained by the process described inGB-A-1157515. The crude hydrolysate is mixed in water with 15 g ofcitric acid and 25 ml of 20% aqueous ammonia. A silane such asγ-aminopropyltriethoxysilane is added to the aqueous solution to providea binder for mineral wool.

EXAMPLE2 Binder Composition Containing Hydrol

100 g of hydrol from the refining process of making a glucose syruphaving a DE of 73, a concentration of 73% by weight of dry substance and50% sugars, 6.0% ash, 2.5% sodium, 3.0% chlorine is treated to removesalts and then mixed in water with 15 g of citric acid and 25 ml of 20%aqueous ammonia γ-aminopropyltriethoxysilane is added to the aqueoussolution to provide a binder for mineral wool.

EXAMPLE3 Binder Composition Containing Wood Molasses

100 g of wood molasses having a concentration of 65% by weight of drysubstance and 55% sugars, 5.0% ash, 0.8% calcium, 0.05% phosphorous,0.04% potassium and substantially no chlorine or sodium, is mixed inwater with 15 g of citric acid and 25 ml of 20% aqueous ammonia.γ-aminopropyltriethoxysilane is added to the aqueous solution to providea binder for mineral wool.

EXAMPLE4 Binder Composition Containing a Crude Starch Hydrolysate

100 g of crude starch hydrolysate having a concentration of 70% byweight of dry substance is mixed in water. 30 g of a batch of a reactionproduct mixture is added made by the following procedure: 82 kg ofdiethanolamine (DEA) is charged in a 400 l reactor and heated to 60° C.Then, a first portion of 72 kg of tetrahydrophthalic anhydride (THPA) isadded. After raising the temperature and keeping it at 130° C. for 1hour, 75 kg of trimellitic anhydride (TMA) and a second portion of 50 kgof THPA are added. The reaction mixture is cooled to 95° C., water isadded and the mixture is stirred for 1 hour. A silane such asγ-aminopropyltriethoxysilane is added to the aqueous solution of thecrude starch hydrolysate and the reaction product mixture to provide abinder for mineral wool.

EXAMPLE5

The binders of Examples 1-4 are used in the production of rock woolinsulating products by spraying the binder solutions through nozzlesnear the cascade rotor apparatus into the formed cloud of fibers in theforming chamber. The coated fibers are collected on transport conveyorsand transferred into a curing oven for a curing time of 5 minutes at acuring temperature of 225° C.

The mineral wool product obtained has a density of about 100 kg/m³, athickness of 120 mm and a binder content of 7% (Loss on Ignition LOI),

EXAMPLE6 Preparation of Resin/Binder Component B1

158 g of diethanolamine are placed in a 1-litre glass reactor providedwith a stirrer and a heating/cooling jacket. The temperature of thediethanolamine is raised to 60° C. whereafter 91 g of tetrahydrophthalicanhydride are added. After raising the temperature and keeping it at130° C., a second portion of 46 g of tetrahydrophthalic anhydride isadded followed by 86 g of trimellitic anhydride. After reacting at 130°C. for 1 hour, the mixture is cooled to 95° C. and 210 g of water addedand the mixture stirred for 1 hour. After cooling to ambienttemperature, the obtained resin is ready for use.

Based upon the above obtained resin a binder is made from the resin byaddition of ammonia to pH 6.5 and 2% of hypophosphorous acid. The solidscontent of the binder was measured as 53% at 200° C., 1 hour.

Preparation of Mixtures of B1 and a Sugar

The binder compositions shown in Table 1 were tested.

TABLE 1 Dextrose Equivalent Binder composition (DE) of sugar syrup 100%B1 (not defined) 50% B1 + 50% Mylose 120 25-32 50% B1 + 50% Mylose 66142 50% B1 + 50% Glucoplus 361 62 50% B1 + 50% Glucosweet 660 73-79 50%B1 + 50% Sirodex 331 95 50% B1 + 50% Dextrose 100 

All percentages are wt. % dry matter

The sugar syrups are all trademarks and available from Syral.

The sugar preparations in Table 1 are made by mixing the followingcomponents:

Binder Solids content Component B1 of sugar Amount of sugar (g) Sugar 1h at 200° C. (g) 100 Mylose 120 68.6% 77.3 100 Mylose 661 76.8% 69.0 100Glucoplus 361 70.9% 74.8 100 Glucosweet 660 66.5% 79.7 100 Sirodex 33160.1% 88.2 100 Dextrose   56% 94.6

All of the above binders were mixed with a standard silane(gamma-aminopropyl-triethoxysilane) in an amount of 1.4% of the totalsolids Finally, the binders were diluted with water to 15% or 20%solids.

Humidity Resistance

A humidity resistance test was carried out by applying the bindercomposition to a filter made of quartz fibers. The sample with binderwas cured in 6 minutes at 200° C., the weight of the cured sample wasmeasured, and then the sample was placed in a chamber with a controlledatmosphere of 95% humidity at 70° C. The weight of the sample was thenmeasured again after 14 days. The weight gain of the sample is ascribedto a water uptake from the water vapor in the chamber.

The relative weight uptake was calculated and is depicted as apercentage value in FIG. 1 for each sample along with the correspondingdextrose equivalent value DE, provided by Syral. The standard deviationsalong with the percentage values are shown in Table 2

TABLE 2 Water Standard deviation Binder composition uptake (%) of 6measurements 100% B1 (*)  3 weeks 11.2 2.8 10 weeks 21.9 3.5 14 weeks42.2 4.3 50% B1 + 50% Mylose  3 weeks 22.4 2.9 120 10 weeks 29.0 2.8 14weeks 60.7 4.0 50% B1 + 50% Mylose  3 weeks 33.1 1.6 661 10 weeks 43.61.5 14 weeks 47.9 2.2 50% B1 + 50%  3 weeks 12.9 3.5 Glucoplus 361 10weeks 15.3 2.2 14 weeks 35.2 8.2 50% B1 + 50%  3 weeks 20.1 2.0Glucosweet 660 10 weeks 29.4 1.7 14 weeks 32.2 1.7 50% B1 + 50%  3 weeks23.8 4.4 Sirodex 331 10 weeks 35.7 4.5 14 weeks 39.1 4.4 50% B1 + 50%Dextrose  3 weeks 23.7 2.2 10 weeks 35.7 1.4 14 weeks 39.6 0.9

It can be seen that there is less water uptake for the bindercompositions containing the sugar syrups Glucoplus 361 and Glucosweet660 having DE-values of 62 and 76 (average value 73-79), respectively,is compared to the water uptake for binder compositions having bothlower DE-values of 25-42 and higher DE-values of 95-100. The wateruptake is a measure of the humidity resistance

Mechanical Strength

Mechanical strength was tested in a so-called grit bar test. Severalbars are manufactured in a moulding process for mechanical testing. Thetest bars consist of a mixture of binder and stone wool shots from thestone wool spinning production. The shots are particles having the samemelt composition as the stone wool fibers, and the shots are normallyconsidered a waste product from the spinning process. The shots used forthe test bar composition have a size of 0.25-0.50 mm. Approximately 90 gof binder with a dry weight content of 15% are mixed with 450 g of shotsand moulded into 8 test bars.

The bars measure 140 mm×25 mm×5 mm.

The test bars are cured for 2 hours at 250° C.

The test bars are subjected to a 3-point bending test in a bendingstrength apparatus with the following settings of a velocity of 10mm/min, a load of 1.0 kN and a span between support of bars of 10 cm.The strengths are reported in N/mm².

A measured value of approx 4.3 N/mm² is considered to provide asufficient binder strength. The standard deviations along with thepercentage values are shown in Table 3.

TABLE 3 Standard deviation Strength of 6 measurements Binder composition(N/mm²⁾ (N/mm²) 100% B1 (*) 4.68 0.39 50% B1 + 50% Mylose 120 5.99 0.9250% B1 + 50% Mylose 661 5.66 0.66 50% B1 + 50% Glucoplus 361 5.09 0.5250% B1 + 50% Glucosweet 660 5.94 0.73 50% B1 + 50% Sirodex 331 5.4 0.950% B1 + 50% Dextrose 5.34 0.8

The measured strengths of all binder compositions are found to besufficient. All sugar-containing samples had a value slightly higherthan the reference value of the B1 binder of 4.68 N/mm².

What is claimed is:
 1. An aqueous binder composition, wherein thecomposition comprises: (a) a sugar syrup comprising a reducing sugar andhaving a dextrose equivalent DE of at least 50 and less than 85; (b) apolycarboxylic acid component; (c) an amine component; and, optionally,(d) a reaction product of a polycarboxylic acid component (b) and anamine component (c).
 2. The aqueous binder composition of claim 1,wherein sugar syrup (a) has a dextrose equivalent DE of at least 55 andless than
 80. 3. The aqueous binder composition of claim herein sugarsyrup (a) has a dextrose equivalent DE of at least 60 and less than 75.4. The aqueous binder composition of claim 1, wherein sugar syrup (a) isselected from one or more of high DE glucose syrups, crude hydrolysatesfrom starch-based glucose refining, treated crude hydrolysates fromstarch-based glucose refining, hydrols, and molasses.
 5. The aqueousbinder composition of claim 4, wherein the molasses is selected from oneor more of cane molasses, beet molasses, citrus molasses, and woodmolasses.
 6. The aqueous binder composition of claim 1, wherein sugarsyrup (a) is employed without any prior removal of proteins and/or oils.7. The aqueous binder composition of claim 1, wherein the sugar syrup(a) has been subjected to ion exchange with at least one of a cationicresin and an anionic resin.
 8. The aqueous binder composition of claim1, wherein polycarboxylic acid component (b) is selected from one ormore of dicarboxylic, tricarboxylic, tetracarboxcylic, pentacarboxylic,and like monomeric polycarboxylic acids, anhydrides, salts, andcombinations thereof, as well as polymeric polycarboxylic acids,anhydrides, copolymers, salts, and combinations thereof.
 9. The aqueousbinder composition of claim 8, wherein polycarboxylic acid component (b)is selected from one or more of citric acid, aconitic acid, adipic acid,azelaic acid, butane tricarboxylic acid, butane tetracarboxylic acid,chlorendic acid, citraconic acid, dicyclopentadiene-maleic acid adducts,fully maleated rosin, maleated tall-oil fatty acids, fumaric acid,glutaric acid, isophthalic acid, itaconic acid, maleated rosin oxidizedto alcohol then carboxylic acid, maleic acid, malic acid, mesaconicacid, oxalic acid, phthalic acid, tetrahydrophthalic acid,hexahydrophthalic acid, terephthalic acid, sebacic acid, succinic acid,tartaric acid, aspartic acid, trimellitic acid, pyromellitic acid,trimesic acid, and anhydrides, salts, and combinations thereof.
 10. Theaqueous binder composition of claim 1, wherein amine component (c) isselected from one or more of ammonia, primary amines, secondary amines,alkanolamines, amino acids, and urea.
 11. The aqueous binder compositionof claim 1, wherein polycarboxylic acid component (b) comprises at leastone carboxylic anhydride and amine component (c) comprises at least onealkanolamine.
 12. The aqueous binder composition of claim 1, wherein thecomposition comprises, based on a total weight (dry matter) of bindercomponents (a), (b) and (c); from 50 to 85 percent by weight of sugarsyrup (a); from 5 to 25 percent by weight of polycarboxylic acidcomponent (b); and. from 1 to 8 percent by weight of amine component(c).
 13. The aqueous binder composition of claim 12, whereinpolycarboxylic acid component (b) comprises at least one carboxylicanhydride and amine component (c) comprises at least one alkanolamine.14. The aqueous binder composition of claim 13, wherein sugar syrup (a)has a dextrose equivalent DE of at least 60 and less than
 75. 15. Theaqueous binder composition of claim wherein the composition furthercomprises a curing accelerator.
 16. The aqueous binder composition ofclaim 1, wherein the composition has a pH of 6 or higher.
 17. Theaqueous binder composition of claim 14, wherein the composition has a pHof 6 or higher.
 18. The aqueous binder composition of claim 1, whereinthe composition comprises a reaction product (d).
 19. A method ofproducing a bonded mineral fiber product, wherein the method comprises:fiberizing a mineral melt to form mineral fibers; carrying the formedmineral fibers by a gas stream into a forming chamber; applying athermosetting binder onto the mineral fibers to form coated fibers;depositing the coated fibers as a mineral fiber web on a receiver; andtransferring the mineral fiber web to a curing oven for curing of thebinder and forming a bonded mineral fiber product; the binder comprisingthe aqueous binder composition of claim
 1. 20. A mineral fiber productcomprising mineral fibers in contact with a cured binder composition,wherein the binder composition comprises the aqueous binder compositionof claim 1.